Stable mixtures containing opacifying pigments

ABSTRACT

A number of stable opacifying mixtures are disclosed which contain specific combinations and levels of titanium dioxide, thickeners, and dispersants. These stable mixtures may be employed in a method of making paints using prepaints or as a conventional component in a coating such as a paint, or in other end-uses where opacifying pigments are employed.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Applications Ser.No. 60/183,655 filed Feb. 18, 2000, Ser. No. 60/183,656 filed Feb. 18,2000, and Ser. No. 60/247,639 filed Nov. 10, 2000.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention is related to stable mixtures containing opacifyingpigments and more specifically, to stable mixtures containing selectcombinations and levels of titanium dioxide, a thickener, and adispersant for use in making paint and other end products.

2. Description of Related Art

In co-pending U.S. provisional patent applications Ser. Nos. 60/183,655;60/183,656; and 60/247,639; prepaints and a method of making paints fromthese prepaints is described. One of the prepaints is a mixturecomprising at least one opacifying pigment, typically titanium dioxide.The other two prepaints may contain either an extender pigment or/and anemulsion polymeric binder. A key requirement for the prepaints is theircompatibility with one another so that they may be mixed with each otherin various ratios to make at least one paint line. Another keyrequirement is that the prepaints, whether comprising an opacifyingpigment, an extender pigment, or an emulsion polymeric binder, be stableso that the prepaints may be prepared, shipped, and stored withoutfailing, for example, failure by exhibiting non-homogeneity, syneresis,settling, gelling and/or viscosity changes.

With respect to prepaints containing an opacifying pigment, stabilitycan be a serious problem. This is especially true when one considersthat even the best commercially-available titanium dioxide slurries showsome syneresis (>2% by volume by visual inspection) upon storage andmust be stirred vigorously and for a considerable length of time beforeuse.

Hence, there is a need for stable mixtures containing specificcombinations and levels of titanium dioxide, thickeners, and dispersantsthat may be employed, inter alia, as prepaints in a method of makingpaints or as conventional components in other end-uses where opacifyingpigments are employed, including coatings, impregnants, inks, graphicarts, papers, textiles, caulks, mastics, adhesives, sealants, buildingproducts and leather.

SUMMARY OF THE INVENTION

Various fluid opacifying mixtures based on titanium dioxide areprovided. Some of the mixture are stable and no mixing is required,others are stable with occasional mixing required, and others are stablewith constant mixing required.

As used herein for all the mixtures “lbs/100 gallons” is based on theweight of the dry material, unless otherwise noted.

The following mixtures are stable and require no mixing when formulatedas described below.

Mixture is a fluid opacifying pigment mixture comprising:

-   (a) about 600 to about 1500 lbs/100 gallons of at least one    universal-grade titanium dioxide;-   (b) about 0.2 to about 20 lbs/100 gallons of at least one    hydrophobically-modified ethylene oxide-urethane polymer (HEUR)    thickener selected from the group consisting of:    -   (i) a HEUR having a C₄-C₁₂ hydrophobe and a molecular weight of        about 10,000 to about 200,000;    -   (ii) a HEUR having a C₆-C₃₀ hydrophobe and a molecular weight of        about 10,000 to about 200,000; and    -   (iii) combinations thereof; and-   (c) about 1.5 to about 16 lbs/100 gallons of at least one dispersant    selected from the group consisting of a maleic acid/diisobutylene    copolymer, a butylmethacrylate/methacrylic acid copolymer, and an    acrylic acid—hydroxypropyl acrylate copolymer;

Mixture 2 is a fluid opacifying pigment mixture comprising:

-   (a) about 600 to about 1500 lbs/100 gallons of at least one    interior-grade titanium dioxide;-   (b) about 0.3 to about 5 lbs/100 gallons of at least one    hydrophobically-modified, alkali-soluble or alkali-swellable    emulsion (HASE) thickener having a C₆-C₂₂ hydrophobe and a molecular    weight of about 10,000 to about 7,000,000; and-   (c) about 1.8 to about 23 lbs/100 gallons of at least one dispersant    selected from the group consisting of maleic acid/diisobutylene    copolymer, a butylmethacrylate/methacrylic acid copolymer, and an    acrylic acid—hydroxypropyl acrylate copolymer;

Mixture 3 is a fluid opacifying pigment mixture comprising:

-   (a) about 600 to about 1500 lbs/100 gallons of at least one    interior-grade titanium dioxide;-   (b) about 0.5 to about 3 lbs/100 gallons of at least one    hydroxyalkyl cellulose thickener having a molecular weight of about    10,000 to about 10,000,000; and-   (c) about 1.8 to about 23 lbs/100 gallons of at least one    polyacrylic acid dispersant.

Mixture 4 is a fluid opacifying pigment mixture comprising:

-   (a) about 600 to about 1500 lbs/100 gallons of at least one    universal-grade titanium dioxide;-   (b) about 2 to about 6 lbs/100 gallons of at least one    hydrophobically-modified hydroxyalkyl cellulose thickener having a    molecular weight of about 10,000 to about 10,000,000; and-   (c) about 1.8 to about 23 lbs/100 gallons of at least one    polyacrylic acid dispersant.

Mixture 5 is a fluid opacifying pigment mixture containing:

-   (a) about 600 to about 1500 lbs/100 gallons of at least one    universal-grade titanium dioxide;-   (b) about 0.2 to about 10 lbs/100 gallons of at least one    hydrophobically-modified hydroxyalkyl cellulose thickener having a    molecular weight of about 10,000 to about 10,000,000;-   (c) about 2 to about 10 lbs/100 gallons of at least one    hydrophobically-modified ethylene oxide urethane polymer (HEUR)    thickener having a C₄-C₃₀ hydrophobe and a molecular weight of about    10,000 to about 200,000; and-   (d) about 3.0 to about 22.5 lbs/100 gallons of at least one maleic    acid/diisobutylene copolymer dispersant.

Mixture 6 is a fluid opacifying pigment mixture comprising:

-   (a) about 600 to about 1500 lbs/100 gallons of at least one    universal-grade titanium dioxide;-   (b) about 0.2 to about 10 lbs/100 gallons of at least one    hydrophobically-modified hydroxyalkyl cellulose thickener having a    molecular weight of about 10,000 to about 10,000,000;-   (c) about 2 to about 10 lbs/100 gallons of at least one    hydrophobically-modified ethylene oxide urethane polymer (HEUR)    thickener having a C₄-C₃₀ hydrophobe and a molecular weight of about    10,000 to about 200,000; and-   (d) about 0.5 to about 22.5 lbs/100 gallons of at least one acrylic    acid—hydroxypropyl acrylate dispersant.

The following mixtures are stable with occasional mixing required.

Mixture 7 is a fluid opacifying pigment mixture comprising:

-   (a) about 600 to about 1500 lbs/100 gallons of at least one    universal-grade titanium dioxide;-   (b) about 1 to about 10 lbs/100 gallons of at least one hydroxyalkyl    cellulose thickener having a molecular weight of about 10,000 to    about 10,000,0000 or hydrophobically-modified hydroxyalkyl cellulose    thickener having a molecular weight of about 10,000 to about    10,000,000;-   (c) optionally, about 2 to about 12 lbs/100 gallons of at least one    hydrophobically-modified ethylene oxide urethane polymer (HEUR)    thickener having a C₄-C₃₀ hydrophobe and a molecular weight of about    10,000 to about 200,000 or at least one clay thickener; and-   (d) about 0.5 to about 22.5 lbs/100 gallons of at least one acrylic    acid/hydroxyl propyl acrylate dispersant.

Mixture 8 is a fluid opacifying pigment mixture containing:

-   (a) about 600 to about 1500 lbs/100 gallons of at least one    universal-grade titanium dioxide;-   (b) about 0.3 to about 5 lbs/100 gallons of at least one    hydrophobically-modified, alkali-soluble or alkali-swellable    emulsion (HASE) thickener having a C₆-C₂₂ hydrophobe and a molecular    weight of about 10,000 to about 7,000,000; and-   (c) about 1.2 to about 45 lbs/100 gallons of at least one    polyacrylic acid dispersant.

The following mixtures are stable with constant mixing required. Theyare formulated as described below.

Mixture 9 is a fluid opacifying pigment mixture containing:

-   (a) about 600 to about 1500 lbs/100 gallons of at least one    universal-grade titanium dioxide;-   (b) about 0.5 to about 10 lbs/100 gallons of at least one    hydroxyalkyl cellulose thickener having a molecular weight of about    10,000 to about 10,000,0000 or about 0.5 to about 10 lbs/100 gallons    of a hydrophobically-modified hydroxyalkyl cellulose thickener    having a molecular weight of about 10,000 to about 10,000,000; and-   (c) about 1.2 to about 18 lbs/100 gallons of at least one maleic    acid/diisobutylene dispersant.

Mixture 10 is a fluid opacifying pigment mixture containing:

-   (a) about 600 to about 1500 lbs/100 gallons of at least one    universal-grade titanium dioxide;-   (b) about 0.1 to about 3 lbs/100 gallons of at least one    hydrophobically-modified, alkali-soluble or alkali-swellable    emulsion (HASE) thickener having a C₆-C₂₂ hydrophobe and a molecular    weight of about 10,000 to about 7,000,000; and-   (c) about 0.6 to about 22.5 lbs/100 gallons of at least one acrylic    acid/hydroxyl propyl acrylate dispersant.

Mixture 11 is a fluid opacifying pigment mixture containing:

-   (a) about 600 to about 1500 lbs/100 gallons of at least one    universal-grade titanium dioxide;-   (b) about 0.1 to about 3 lbs/100 gallons of at least one    hydrophobically-modified, alkali-soluble or alkali-swellable    emulsion (HASE) thickener having a C₆-C₂₂ hydrophobe and a molecular    weight of about 10,000 to about 7,000,000; and-   (c) about 0.6 to about 45 lbs/100 gallons of at least one maleic    acid/diisobutylene dispersant.

Mixture 12 is a fluid opacifying pigment mixture containing:

-   (a) about 600 to about 1500 lbs/100 gallons of at least one    interior-grade titanium dioxide;-   (b) about 0.2 to about 20 lbs/100 gallons of at least one    hydrophobically-modified ethylene oxide urethane polymer (HEUR)    thickener selected from the group consisting of:    -   (i) a HEUR having a C₄-C₁₂ hydrophobe and a molecular weight of        about 10,000 to about 200,000;    -   (ii) a HEUR having a C₆-C₃₀ hydrophobe and a molecular weight of        about 10,000 to about 200,000; and    -   (iii) combinations thereof; and-   (c) about 1.2 to about 8 lbs/100 gallons of at least one maleic    acid/diisobutylene dispersant.

All of the above mixtures have a titanium dioxide (TiO₂) pigment volumeconcentration (PVC) of about 40 to 100%, a titanium dioxide (TiO₂)volume solids content of at least about 15%, and a Stormer viscosity ofabout 50 to about 250 KU.

All of the mixtures contain water and may contain optional additivesselected from the group consisting of a defoamer, a surfactant, acoalescent, a base, a biocide, a mildeweide, a co-dispersant, apolymeric binder, a voided latex polymer and combinations thereof.

In order to prepare stable mixtures of opacifying pigments, one mustfollow strict rules in selecting the types and level of specificingredients, using the general approach set out below:

-   -   select the type and level of titanium dioxide based on whether        the final paint will be for exterior or interior use with a        universal-grade being selected for interior, exterior, or        interior/exterior use and with an interior-grade being selected        for interior use only;    -   select the appropriate rheology modifier/thickener based on the        type of titanium dioxide selected;    -   select the appropriate dispersant based on the type of rheology        modifier/thickener selected;    -   determine the level of dispersant necessary to produce a stable        final mixture; and    -   determine the level of rheology modifier/thickener required to        produce a stable final mixture.

As used herein, the term “stable” applies to those mixtures that meetall of the following criteria, as set out in the Stability Testsdescribed below, after being stored at a temperature of at least 120° C.for at least ten (10) days:

-   -   (1) there is less than 2% by volume of syneresis in the mixture        (determined by inspecting the pigment mixture visually)        (referred to herein as “Stability Test 1”).    -   (2) the mixture has a Brookfield viscosity (measured at a shear        rate of 1.25 sec⁻¹) of less than 100,000 centipoise, preferably        less than 50,000 centipoise after cooling to ambient temperature        (22-25° C.), but prior to mechanical shearing (referred to        herein as “Stability Test 2”).    -   (3) the ratio of the Brookfield viscosity (measured at a shear        rate of 1.25 sec⁻¹) after heat aging to the Brookfield viscosity        (measured at a shear rate of 1.25 sec⁻¹) prior to heat aging is        no greater than 3 after the mixture is cooled to ambient        temperature (22-25° C.) and after mechanical shearing using a        propeller-type mixer (referred to herein as “Stability Test 3”).        Commercial titanium dioxide slurries do not pass Stability Test        1 and must be stirred, sometimes constantly, prior to use.        Mixtures having Brookfield viscosities higher than those        specified in Stability Test 2 tend to gell and resist flow and        therefore are difficult to pump in conventional equipment.        Stability Test 3 is used to determine whether or not the mixture        developed, or will develop, a gel network resistant to shear        thinning (mixing) during storage.

The mixing conditions used to categorize the stability of the fluidopacifying pigment mixtures are as follows:

-   (1) mixtures which require no mixing or other form of agitation over    typical storage times (at least 30 days) and under storage    conditions where the temperature can be as high as 140° F. and as    low as 25° F. to remain stable are referred to herein as “stable    with no mixing required”)(require mixing over 0% of storage time);-   (2) mixtures which require periodic or occasional mixing or other    forms of agitation to re-homogenize or break any minimal or slight    structure formed over the typical storage times and conditions    described above are referred to herein as “stable with occasional    mixing required”)(require mixing over >0% of storage time); and-   (3) mixtures which require constant mixing or other forms of    agitation to re-homogenize or break any significant structure formed    over the typical storage times and conditions described above (are    referred to herein as “stable with constant mixing    required”)(require mixing over >50% of storage time).    It should be noted that while the “stable with no mixing required”    condition requires no mixing or other form of agitation to remain    stable, applying some form of mixing or agitation to the mixture    (whether occasional or constant) does not exclude that particular    mixture from the definition of a stable mixture with “no mixing    required”. Likewise, it should be noted that while the “stable with    occasional mixing required” condition requires only occasional    mixing or other form of agitation to remain stable, applying    constant mixing or agitation to the mixture does not exclude that    particular mixture from the definition of a stable mixture with    “occasional mixing required”.

Any type of mixer or agitator may be used such as, but not limited to animpellar, a recirculator, a shaker, a mill, a rotator, a bubbler, asonicator, a pump or a like means suitable to move the mixture aboutitself.

The mixtures herein may be employed as prepaints in systems usingdelayed product differentiation as described in U.S. patent applicationsSer. No. 60/183,655 filed Feb. 18, 2000; Ser. No. 60/183,656 filed Feb.18, 2000; Ser. No. 60/247,639 filed Nov. 10, 2000], as well as employedas replacements for conventional mixtures containing opacifyingpigments, such as titanium dioxide slurries, mill bases, colorantdispersions, coating colors, and the like.

The pigment volume concentration (PVC) is a measure of how “binder-rich”a formulation is. It is calculated using the formula:${{PVC}(\%)} = {\frac{\left( {{{volume}\quad{of}\quad{{pigment}(s)}} + {{volume}\quad{{extender}(s)}}} \right)}{\left( {{{volume}\quad{of}\quad{{pigment}(s)}} + {{volume}\quad{{extender}(s)}} + {{volume}\quad{{binder}(s)}}} \right.} \times 100}$

The volume solids content (VS) is the dry volume of pigment(s) plus thedry volume of extender(s) plus the dry volume of binder(s). It iscalculated using the formula: ${{VS}(\%)} = {\frac{\begin{matrix}{{{dry}\quad{volume}\quad{of}\quad{{pigment}(s)}} +} \\{{{dry}\quad{volume}\quad{of}\quad{{extender}(s)}} + {{dry}\quad{volume}\quad{of}\quad{{binder}(s)}}}\end{matrix}}{{total}\quad{volume}\quad{of}\quad{formulation}} \times 100.}$

If additives are present, their volumes are not included in determiningthe total dry volume.

The titanium dioxide pigment volume concentration (TiO₂ PVC) is ameasure of how “binder-rich” a formulation is relative to only thetitanium dioxide (TiO₂) content. It is calculated using the formula:${{TiO}_{2}{{PVC}(\%)}} = {\frac{{volume}\quad{of}\quad{TiO}_{2}{\quad\quad}{{pigment}(s)}}{\left( {{{volume}\quad{of}\quad{{pigment}(s)}} + {{volume}\quad{{extender}(s)}} + {{volume}\quad{{binder}(s)}}} \right.} \times 100}$

The titanium dioxide volume solids content (TiO₂ VS) is the dry volumeof TiO₂ pigment(s) plus the dry volume of extender(s). It is calculatedusing the formula:${{TiO}_{2}{{VS}(\%)}} = {\frac{{dry}\quad{volume}\quad{of}\quad{TiO}_{2}\quad{{pigment}(s)}}{{total}\quad{volume}\quad{of}\quad{formulation}} \times 100.}$If additives are present, their volume is not included in determiningthe total dry volume.Opacifying Pigments

Suitable opacifying pigments include:

-   (1) white pigments which impart white scattering power to a paint    across all visible wave lengths without a high degree of absorption;    and-   (2) auxiliary hiding pigments including inorganic and organic solids    or voided latex polymers which do not impart a primary color or    hiding power to a paint although they may have secondary influences    on those properties.

Such opacifying pigments include titanium dioxide or a combination oftitanium dioxide and auxiliary hiding pigments such as voided latexpolymer particles, zinc oxide, lead oxide, a synthetic polymer pigment,and mixtures thereof. Rutile and anatase grades of titanium dioxide aresuitable for use herein. Rutile titanium dioxide is preferred. Thesurface of the titanium dioxide may be treated with various organic orinorganic surface treatments, e.g., the oxides of silica, alumina, andzirconia. Fumed titanium oxide is also useful herein.

For specific mixtures, certain grades of titanium dioxide are required.For example, for some of the mixtures universal-grade titanium dioxidemay be used, whereas for others interior-grade titanium dioxide must beused. As used herein, “universal-grade” titanium dioxide means titaniumdioxide that is suitable for use in both interior and exteriorapplications and which is typically treated with oxides of alumina(about 1 to about 7%), silica (up to about 15%) and zirconia (up toabout 15%). As used herein, “interior-grade” titanium dioxide meanstitanium dioxide that is only suitable for use in interior applicationswhich is typically treated with only the oxides of alumina (about 1 toabout 7%) or a combinations of the oxides of alumina (about 1 to about7%) with the oxides of silica (up to about 5%). This grade of titaniumdioxide is likely to provide poorer water resistance in final coatingsthan the universal-grade titanium dioxide).

The voided latex particles useful herein have a particle size diameterof about 100 nm to about 2,500 nm and a void fraction of about 10% toabout 75%. Preferably, the particles have a particle size of about 500run to about 1,100 nm. The particles must have at least one void, butthey may have multiple voids, non-spherical voids, interconnected voids,voids having channels connected to the outside of the particles, andthey can encompass structures described as vesiculated and sponge-like.Preferably, the particles have a single void. They have a glasstransition temperature (Tg), as measured by differential scanningcalorimetry at a rate of 20° C./minute, of at least about 20° C.,preferably at least about 50° C. The higher the Tg, the harder theparticle is and the less likely it is to collapse. If the particlescollapse, they are unable to contribute to hiding. The voided latexparticles may be prepared by conventional polymerization processes knownin the art, such as those disclosed in U.S. Pat. Nos. 3,784,391,4,427,836; 4,469,825; 4,594,363; 4,798,691; 4,880,842; 4,908,271;4,972,000; 5,041,464, 5,157,084; 5,216,044, 5,494,971; 5,545,695; and6,020,435, as well as Japanese Patent Applications 60/223,873, 61/62510,61/66710, 61/86941, 62/127336, 62/156387, 01/185311, and 02/140272.

Thickener

Suitable thickeners include both non-associative,water-soluble/water-swellable thickeners and associative thickeners.Suitable non-associative, water-soluble/water-swellable thickenersinclude polyvinyl alcohol (PVA), alkali soluble or alkali swellableemulsions known in the art as ASE emulsions, and cellulosic thickenerssuch as hydroxyalkyl celluloses including hydroxymethyl cellulose,hydroxyethyl cellulose and 2-hydroxypropyl cellulose, sodiumcarboxymethyl cellulose (SCMC), sodium carboxymethyl cellulose,2-hydroxyethyl cellulose, 2-hydroxypropyl methyl cellulose,2-hydroxyethyl methyl cellulose, 2-hydroxybutyl methyl cellulose,2-hydroxyethyl ethyl cellulose, and the like. Suitable associativethickeners include hydrophobically-modified, alkali-soluble emulsionsknown in the art as HASE emulsions, hydrophobically-modified ethyleneoxide-urethane polymers known in the art as HEUR thickeners,hydrophobically-modified cellulosics such as hydrophobically-modifiedhydroxyethyl cellulose, hydrophobically-modified polyacrylamides, andthe like. Also useful as thickeners are fumed silica, attapulgite clayand other types of clay, titanate chelating agents, and the like.

Suitable dispersants include anionic polymers such as homopolymers andcopolymers based on polycarboxylic acids, including those that have beenhydrophobically- or hydrophilically-modified, e.g., polyacrylic acid,polymethacrylic acid, maleic anhydride and copolymers thereof with eachother and with various monomers such as styrene, acrylate ormethacrylate, diisobutylene, and other hydrophilic or hydrophobiccomonomers. Suitable dispersants further include salts of the abovedispersants and mixtures thereof.

The opacifying mixtures may include certain optional additives includingdefoamers, surfactants, coalescents, biocides, mildewcides,co-dispersants, dispersing resins, latex adsorbing resins, polymericbinders, and the voided latex polymers (described above).

Suitable defoamers include silicone-based and mineral oil-baseddefoamers and the like.

Suitable surfactants include cationic, anionic and non-ionicsurfactants.

Suitable coalescents, plasticizers, and other optional solvents includeethylene glycol, propylene glycol, hexylene glycol,2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (TEXANOL™), glycolethers, mineral spirits, methyl carbitol, butyl carbitol, phthalates,adipates, and the like.

Suitable mildewcides and biocides include zinc oxide, isothiazolones,triazoles, and the like.

Suitable co-dispersants include non-ionic, anionic, and cationicdispersants such as 2-amino 2-methyl 1-propanol, dimethyl amino ethanol,potassium tripolyphosphate, trisodium polyphosphate, citric acid andother carboxylic acids, and the like.

Latex polymer binders are polymers or prepolymers which form the primaryfilm of a paint. They bind the pigment and/or extenders, provide therequired paint flow, and determine the gloss and hardness of the finalpaint film. The binder selected will depend upon the final use of theformulated paints. Binders suitable for exterior paints are generallysuitable for interior paints, but binders suitable for interior paintsmay not be suitable for exterior paints. Suitable binders include, butare not limited to, homopolymers, copolymers, or terpolymers such as,for example, polyvinyl acetate, styrene-acrylic, styrene-butadiene,vinyl acetate-acrylic, ethylene-vinyl acetate, vinyl acetate-vinylversatate, vinyl acetate-vinyl maleate, vinyl acetate-vinylchloride-acrylic, ethylene-vinyl acetate-acrylic, and urethane polymers,optionally containing up to 10% by weight of functional groups (forexample, but not limited to, carboxylic acid, phosphate, sulfate,sulfonate, amide and combinations thereof), other non-functionalmonomers, and mixtures thereof.

DETAILED DESCRIPTION OF THE INVENTION

All ranges disclosed herein are inclusive and the minimums and maximumsof the nested ranges are combinable. All levels are in dry pounds/100gallons i.e., pounds of solids/100 gallons of the mixtures unlessotherwise noted. After the required ingredients and optional ingredientsare combined, sufficient water is added to give a total of 100 gallonsof the mixture.

The following optional ingredients may be included in any of thecombination ranges shown below:

Optional Ingredients Preferred Preferred Ingredient Types Types LevelLevel Defoamer any solvent- 1-5 2-3 based, silicone- based Surfactantnonionic, nonionic, 1-7 1-5 anionic, cationic anionic Solvent andpropylene glycol, propylene  1-200  1-100 coalescent ethylene glycol,glycol, hexylene glycol, Texanol ® 2,2,4-trimethyl-1-3- pentanediolmonoisobutyrate (Texanol ®), butyl carbitol, methyl carbitol, mineralspirits, Base ammonium ammonium up to 10 up to 5  hydroxide, hydroxide,sodium hydroxide, AMP-95 potassium hydroxide, 2-amino 2-methyl1-propanol (AMP) Biocide isothiazolones, iso- up to 5  up to 3 carbamates, thiazolones thiazoles, phthalonitriles, dioxanes,hydantoins, carbanilides, triazines, ureas, thiocyanates Mildewcideisothiazolones, iso- up to 20 up to 10 carbamates, thiazolonesthiazoles, phthalonitriles, dioxanes, hydantoins, carbanilides,triazines, ureas, thiocyanates Co- 2-amino 2-methyl citric acid, up to5  up to 2  dispersant 1-propanol KTTP, AMP (AMP-95), dimethyl aminoethanol (DMEA), potassium tripolyphosphate (KTTP), trisodiumpolyphosphate (TSPP), Polymeric See above vinyl acrylic,  up to 150 upto 80 Binder description vinyl acetate, styrene acrylic Voided latex Seeabove x  up to 100 up to 60 polymer descriptionCombination No. 1

The combinations shown below do not require mixing to remain stable.They are exemplified in Example 1.

Ingre- Preferred Preferred dients Types Types Level Level Dis- MA/DIB,MA/DIB 1.5-16  3.7-14  persant BMA/MAA, AA/HPA, SMA Thick- HEUReffective HEUR 0.2-20  10-16 ener hydrophobe effective C₄-C₁₂ MWhydrophobe 10,000-200,000, C₄-C₁₂ and MW 12,000- 150,000 HEUR effectiveHEUR 0.8-5   0.2-2   hydrophobe effective C₆-C₃₀ MW hydrophobe10,000-200,000, C₆-C₂₄ and or combinations MW 12,000- thereof 150,000TiO₂ Universal grade Universal TiO₂  600-1500  700-1400 coated withcoated with 1%-7% Al₂O₃, 1.5-5% Al₂O₃ up to 15% SiO₂ 1.2-12% SiO₂, up to15% ZrO₂ up to 4% ZrO₂Combination No. 2

The following combinations do not require mixing to remain stable. Theyare exemplified in Example 2.

Ingre- Preferred Preferred dients Types Types Level Level Dis- MA/DIB,PAA 1.8-23   3.5-16.8 persant BMA/MAA, AA/HPA, PAA Thick- HASE effectiveHASE effective 0.3-5   1-3 ener hydrophobe hydrophobe C₆-C₂₂ MW C₆-C₁₈and 10,000-7,000,000 MW 100,000- 5,000,000 TiO₂ Interior grade Interiorgrade  600-1500  700-1400 coated with coated with 1-7% Al₂O₃/ 2-5%Al₂O₃/ 0-5% SiO₂ 0-5% 0-3% SiO₂Combination No. 3

The following combinations do not require mixing to remain stable. Theyare exemplified in Example 3.

Ingre- Preferred Preferred dients Types Types Level Level Dis- PAA PAA1.8-23   3.5-16.8 persant Thick- Hydroxy- Hydroxyethyl 0.5-3   1-2 eneralkylcellulose and cellulose combinations MW 100,000- thereof MW2,000,000 10,000- 10,000,000 TiO₂ Interior grade Interior grade 600-1500  700-1400 coated with coated with 1-7% Al₂O₃ 2-5% Al₂O₃/ up to5% SiO₂ up to 3% SiO₂Combination No. 4

The following combinations do not require mixing to remain stable. Theyare exemplified in Example 4.

Ingre- Preferred Preferred dients Types Types Level Level Dis- PAA PAA1.8-23   3.5-16.8 persant Thick- Hydrophobically- Hydro- 2-6 3-5 enermodified phobically- hydroxy- modified alkyllcellulose hydroxy- MW10,000- ethylcellulose 10,000,000 MW 50,000- 2,000,000 TiO₂ Universalcoated Universal  600-1500  700-1400 with 1-7% coated with Al₂O₃, 1.5-5%Al₂O₃, up to 15% SiO₂, 1.2-12% SiO₂, up to 15% ZrO₂ up to 4% ZrO₂Combination No. 5

The following combinations do not require mixing to remain stable. Theyare exemplified in Example 5.

Ingre- Preferred Preferred dients Types Types Level Level Dis- MA/DIB orMA/DIB or  3.0-22.5  5.6-16.8 persant AA/HPA AA/HPA MA/DIB MA/DIB 0.5-22.5 2.8-14  AA/HPA AA/HPA Thick- Hydrophobically- Hydro- 0.2-10 0.5-5   ener modified phobically- hydroxyalkyl modified cellulosehydroxyethyl MW 10,000- cellulose 10,000,000 MW 50,000- 2,000,000 Thick-HEUR effective HEUR  2-10  5-10 ener hydrophobe effective C₄-C₃₀hydrophobe MW 10,000- C₆-C₂₄ 200,000 MW 12,000- 150,000 TiO₂ Universalcoated Universal  600-1500  700-1400 with 1-7% coated with Al₂O₃, 1.5-5%Al₂O₃, up to 15% SiO₂, 1.2-12% SiO₂, up to 15% ZrO₂ up to 4% ZrO₂Combination No. 6

The following combinations requires occasional mixing to remain stable.They are exemplified in Example 6.

Ingre- Preferred Preferred dients Types Types Level Level Dis- AA/HPAAA/HPA 0.5-22.5 2.8-14   persant Thick- Hydrophobically- Hydro- 1-102-7  ener modified phobically- hydroxyalkyl modified cellulosehydroxyethyl MW 10,000- cellulose 1,000,000 MW 50,000- or 1,000,000Hydroxyethyl Hydroxyethyl 1-10 2-7  cellulose cellulose MW 10,000- MW100,000- 1,000,000 1,000,000 or combinations of the above orcombinations of 2-12 4-10 the above with: HEUR effective HEUR 2-12 3-6 hydrophobe effective C₄-C₃₀ hydrophobe MW 10,000- C₆-C₂₄ 200,000 MW12,000- or 150,000 attapulgite clay TiO₂ Universal coated Universal600-1500 700-1400 with 1.0-7% coated with Al₂O₃, 1.5-5% Al₂O₃, up to 15%SiO₂, 1.2-12% SiO₂, up to 15% ZrO₂ up to 4% ZrO₂Combination No. 7

The following combinations requires occasional mixing to remain stable.They are exemplified in Example 7.

Ingre- Preferred Preferred dients Types Types Level Level Dis- PAA PAA1.2-45  3.5-28  persant Thick- HASE effective HASE effective 0.3-5  1.0-3   ener hydrophobe hydrophobe C₆-C₂₂ C₆-C₁₈ MW 10,000- MW 100,000-7,000,000 5,000,000 TiO₂ Universal coated Universal  600-1500  700-1400with 1-7% coated with Al₂O₃, 1.5-5% Al₂O₃, up to 15% SiO₂, 1.2-12% SiO₂,up to 15% ZrO₂ up to 4% ZrO₂Combination No. 8

The following combinations requires constant mixing to remain stable.They are exemplified in Example 8.

Ingre- Preferred Preferred dients Types Types Level Level Dis- MA-DIBMA-DIB 1.2-18  3.5-14  persant Thick- Hydrophobically- Hydro- 0.5-10 0.5-8   ener modified phobically- hydroxyalkyl modified cellulosehydroxyethyl MW 10,000- cellulose 1,000,000 MW 50,000- or 1,000,000Hydroxyethyl Hydroxyethyl cellulose cellulose MW 10,000- MW 100,000-1,000,000 1,000,000 or combinations of the above TiO₂ Universal coatedUniversal  600-1500  700-1400 with 1-7% coated with Al₂O₃, 1.5-5% Al₂O₃,up to 15% SiO₂, 1.2-12% SiO₂, up to 15% ZrO₂ up to 4% ZrO₂Combination No. 9

The following combinations requires constant mixing to remain stable.

Ingre- Preferred Preferred dients Types Types Level Level Dis- AA/HPAAA/HPA  0.6-22.5 2.8-14  persant Thick- HASE effective HASE effective0.1-3   0.3-2   ener hydrophobe hydrophobe C₆-C₂₂ C₆-C₁₈ MW 10,000- MW100,000- 7,000,000 5,000,000 TiO₂ Universal coated Universal  600-1500 700-1400 with 1-7% coated with Al₂O₃, 1.5-5% Al₂O₃, up to 15% SiO₂,1.2-12% SiO₂, up to 15% ZrO₂ up to 4% ZrO₂Combination No. 10

The following combinations will require constant mixing to remainstable.

Ingred- Preferred Preferred ients Types Types Level Level DispersantMA/DIB MA/DIB 0.6-45  2.8-21  Thickener HASE effective HASE effective0.1-3   0.3-2   hydrophobe hydrophobe C₆-C₂₂ MW C₆-C₁₈ MW 10,000-100,000- 7,000,000 5,000,000 TiO₂ Universal coat- Universal coat- 600-1500  700-1400 ed with 1-7% ed with 1.5-5% Al₂O₃, up to Al₂O₃, 15%SiO₂, up 1.2-12% SiO₂, to 15% ZrO₂ up to 4% ZrO₂Combination No. 11

The following combinations require constant mixing to remain stable.

Ingred- Preferred Preferred ients Types Types Level Level DispersantMA/DIB MA/DIB 1.2-18  3.5-14  Thickener HEUR effec- HEUR effec- 0.2-20 10-16 tive hydro- tive hydro- phobe C₄-C₁₂ phobe C₄-C₁₂ MW 10,000- MW12,000- 200,000 or 150,000 HEUR effec- HEUR effec- 0.8-5   0.2-2   tivehydro- tive hydro- phobe C₆-C₃₀ phobe C₆-C₂₄ average MW MW 12,000-10,000- 150,000 200,000 or combinations thereof TiO₂ Interior gradeInterior grade  600-1500  700-1400 coated with coated with 1-7% Al₂O₃,2-5% Al₂O₃, up to 5% SiO₂ up to 3% SiO₂

Test Procedures

The Stormer viscosity of the mixtures is measured using ASTM methodD562.

The Brookfield viscosity of the mixtures is measured using spindle #4 ofa Brookfield viscometer at 6 rpm.

The ICI viscosity of the mixtures is measured using ASTM methodD3205-77.

In the following examples, the mixtures may be prepared using alaboratory mixer having a 45° pitch stirring blade. The water andoptional dispersant, defoamer, surfactant and/or biocide are combinedand mixed. The titanium dioxide slurry is slowly added and the mixtureis stirred for 15-20 minutes. The binder and optional coalescent,rheology modifier, ammonia, and additional water, if necessary, are thenadded.

In the above description and in the examples, the followingabbreviations are used:

Abbreviations AA Acrylic acid PAA Polyacrylic acid MA/DIB Maleicacid/diisobutylene copolymer AA/HPA Acrylic acid/hydroxypropyl acidBMA/MAA Butylmethacrylate/methacrylic acid copolymer SMA Styrene oralpha methylstyrene/alkylacrylate (optional)/ methacrylic or acrylicacid copolymers or terpolymers HEC Hydroxyethyl cellulose HMHECHydrophobically-modified HEC HEUR Hydrophobically-modified ethyleneoxide-based urethane block copolymers HASE Hydrophically-modified alkalisoluble emulsions TiO₂ Titanium dioxide Al₂O₃ Alumina or oxide ofaluminum SiO₂ Silica or oxide of silicon ZrO₂ Zirconium dioxide cpscentipoises MW molecular weight as measured by gel permeationchromatography

EXAMPLES Example 1

Mixtures A to E described below will require no mixing to remain stable.

A Ingredients lbs/100 gallons Grind prepared on Cowles disperser Water258.35 Propylene glycol 50 Tamol ™ 731 MA/DIB 53.42 dispersantFoamaster ® VL defoamer 1.50 Triton CF-10 surfactant 2.00 Kathon ® LX1.5% 2.00 biocide Ti-Pure ® R706 universal- 1335.56 grade TiO₂ Letdownprepared on Cowles disperser Ammonia hydroxide 0.6 (28%) Foamaster ® VLdefoamer 1.50 Acrysol ® RM-2020NPR 30.00 HEUR thickener Letdown (on lowspeed mixer) Acrysol ® RM-2020NPR 40.40 HEUR thickener Water 68.96 KUinitially after 90 preparation pH initially after 9.20 preparation ICIinitially after 2.8 preparation Brookfield viscosity 2500 (cps at 1.25sec⁻¹) Actual scale prepared 50 (gallons) B C D E lbs/100 lbs/100lbs/100 lbs/100 Ingredients gallons gallons gallons gallons Grindprepared on Cowles disperser Water 130 130 130 130 Propylene glycol 5050 50 50 Tamol ® 731 MA/DIB 29.38 29.38 29.38 29.38 dispersantFoamaster ® VL 3.00 3.00 3.00 3.00 defoamer Triton CF-10 surfactant 2.002.00 2.00 2.00 Kathon ® LX 1.5% 2.00 2.00 2.00 2.00 biocide Ti-Pure ®R-706 734.56 734.56 734.56 734.56 universal-grade TiO₂ Rhoplex ® SG-10M151.20 151.20 151.20 151.20 acrylic binder Texanol ® coalescent 12.512.5 12.5 12.5 Ammonium hydroxide 0.60 0.60 0.60 0.60 (28%) Ropaque ®Ultra opaque 164.44 164.44 164.44 164.44 polymer Acrysol ® RM- 30 30 3030 2020NPR HEUR thickener Letdown prepared on low speed mixer)Co-thickener type Acrysol ® Acrysol ® Acrysol ® Acrysol ® RM- RM-825SCT-275 RM-12W 2020NPR HEUR HEUR HEUR HEUR Level of co-thickener 33.52.24 2.63 4.84 water 60.0 91.2 90.8 88.5 KU initially after 93 99 96 96preparation pH initially after 8.80 8.78 8.76 8.74 preparation ICIinitially after 3.0 1.7 1.8 1 7 preparation Brookfield viscosity 30103710 6010 24000 (cps at 1.25 sec⁻¹) Actual scale prepared 50 50 50 50(gallons)

Example 2

Mixtures A to G described below will require no mixing to remain stable.

A B C D lbs/100 lbs/100 lbs/100 lbs/100 Ingredients gallons gallonsgallons gallons Grind prepared on Cowles disperser Water 228.00 228.00228.00 228.00 Propylene glycol 50.00 50.00 50.00 50.00 Tamol ® 125438.16 38.16 38.16 38 16 AA/MAA dispersant Triton ® CF-10 2.00 2.00 2.002.00 surfactant Foamaster ® VL 1.50 1.50 1.50 1.50 defoamer Kathon ® LX1.5% 2.00 2.00 2.00 2.00 biocide Ti-Pure ® R900 interior- 1335.521335.52 1335.52 1335.52 grade TiO₂ Letdown prepared on Cowles disperserFoamaster ® VL 1.50 1.50 1.50 1.50 defoamer Water 97.00 97.00 97.0097.00 Ammonium hydroxide 0.4 0.4 0.4 0.4 (28%) Acrysol ® DR-1 HASE 1.01.0 1.0 1.0 thickener Letdown prepared on low speed mixer Acrysol ® DR-1HASE 4.0 5.0 6.0 7.0 thickener Water 83.96 82.96 81.96 80.96 KUinitially after 77 80 83 87 preparation pH initially after 0.4 0.5 0.60.6 preparation ICI initially after 9.06 8.98 8.89 8.79 preparationBrookfield viscosity 12800 14500 15000 16700 (cps at 1.25 sec⁻¹) Actualscale prepared 50 50 50 50 (gallons) E F G lbs/100 gallons lbs/100gallons lbs/100 gallons Grind prepared on Cowles disperser Water 228.00228.00 228.00 Propylene glycol 50.00 50.00 50.00 Tamol ® 1254 38.1638.16 38.16 AA/MAA dispersant Triton ® CF-10 2.00 2.00 2.00 surfactantFoamaster ® VL 1.50 1.50 1.50 defoamer Kathon ® LX 1.5% 2.00 2.00 2.00biocide Ti-Pure ® R900 in- 1335.52 1335.52 1335.52 terior grade TiO₂Letdown prepared on Cowles disperser Foamaster ® VL 1.50 1.50 1.50defoamer Water 97.00 97.00 97.00 Letdown prepared on low speed mixerThickener type Acrysol ® DR- Acrysol ® DR- Acrysol ® DR- 73 HASE 1 HASE3 HASE Level of thickener 6.86 6.08 6.04 Ammonia hydroxide 0.40 0.300.22 (28%) Water 82.08 82.96 83.08 KU initially after 81 81 81preparation pH initially after 0.8 0.6 0.7 preparation ICI initiallyafter 9.01 8.96 8.99 preparation Brookfield viscosity 15700 15300 15200(cps at 1.25 sec⁻¹) Actual scale prepared 50 50 50 (gallons)

Example 3

Mixture A described below will require no mixing to remain stable.

A Ingredients lbs/100 gallons Grind prepared on Cowles disperser Water228.00 Propylene glycol 50.00 Tamol ® 1254 AA/MAA dispersant 38.16Triton ® CF-10 surfactant 2.00 Foamaster ® VL defoamer 1.50 Kathon ® LX1.5% biocide 2.00 Ti-Pure ® R900 interior-grade TiO₂ 1335.52 Letdownprepared of Cowles disperser Foamaster ® VL defoamer 1.50 Water 97.00Letdown prepared on low speed mixer Natrosol ® 250 MHR (3.5% solution in41.16 water) HEC thickener Water 48.18 KU initially after preparation 80pH initially after preparation 0.6 ICI initially after preparation 9.37Brookfield viscosity 15100 (cps at 1.25 sec⁻¹) Actual scale prepared(gallons) 50

Example 4

Mixture A described below will require no mixing to remain stable.

A Ingredients lbs/100 gallons Grind prepared on Cowles disperser Water168.76 Propylene glycol 62.5 Tamol ® 1254 AA/MAA dispersant 26.24Foamaster ® VL defoamer 1.88 Triton ® CF-10 surfactant 2.50 Kathon ® LX1.5% biocide 2.50 Ti-Pure ® R902 universal-grade TiO₂ 918.2 Letdownprepared on Cowles disperser Foamaster ® VL defoamer 1.88 Ropaque ®Ultra opaque polymer 205.56 Letdown prepared on a low speed mixerNatrosol ® Plus 430 (4% in solution in 89.52 water) HMHEC thickenerAmmonia hydroxide (28%) 0.46 Water 55.46 KU initially after preparation97 pH initially after preparation 8.77 ICI initially after preparation1.0 Brookfield viscosity 18000 (cps at 1.25 sec⁻¹) Actual scale prepared(gallons) 50

Example 5

Mixtures A to C described below will require no mixing to remain stable.

A Ingredients lbs/100 gallons Grind prepared on Cowles disperser Water160 Propylene glycol 50 Tamol ® 1124 AA/HPA dispersant 7.35 Kathon ® LX1.5% biocide 2.00 Ti-Pure ® R706 universal-grade TiO₂ 918.2 Letdownprepared on Cowles disperser Foamaster ® VL defoamer 1.5 Ropaque ® Ultraopaque polymer 205.56 Acrysol ® RM-2020NPR HEUR 40.0 thickenerNatrosol ® Plus 330 (3% in solution in 68.32 water) HMHEC thickenerAmmonium hydroxide (28%) 2.16 Water 76.3 KU initially after preparation98 pH initially after preparation 8.73 ICI initially after preparation1.3 Brookfield viscosity 18500 (cps at 1.25 sec⁻¹) Actual scale prepared(gallons) 50 B Ingredients lbs/100 gallons Grind prepared on Cowlesdisperser Water 130 Propylene glycol 50 Tamol ® 731 MA/DIB dispersant29.38 Foamaster ® VL defoamer 1.50 Triton ® CF-10 surfactant 2.00Kathon ® LX 1.5% biocide 2.00 Ti-Pure ® R706 universal-grade TiO₂ 734.56Letdown prepared on Cowles disperser Rhoplex ® SG-10M acrylic binder151.20 Texanol ® coalescent 12.5 Ammonium hydroxide (28%) 0.60 Ropaque ®Ultra opaque polymer 164.44 Foamaster ® VL defoamer 1.50 Acrysol ®RM-2020NPR HEUR 30.00 thickener Letdown prepared on low speed mixerNatrosol ® Plus 330 (3% in solution in 27.6 water) HMHEC thickener Water65.82 KU initially after preparation 98 pH initially after preparation8.73 ICI initially after preparation 1.9 Brookfield viscosity 10800 (cpsat 1.25 sec⁻¹) Actual scale prepared (gallons) 50 C Ingredients lbs/100gallons Grind prepared on Cowles disperser Water 130 Propylene glycol 50Tamol ® 731 MA/DIB dispersant 30.04 Foamaster ® VL defoamer 1.50Triton ® CF-10 surfactant 2.00 Kathon ® LX 1.5% biocide 2.00 Kronos ®2102 universal-grade TiO₂ 751.09 Rhoplex ® SG-10M acrylic binder 151.2Texanol ® coalescent 12.49 Ammonia hydroxide (28%) 0.60 Ropaque ® Ultraopaque polymer 164.44 Foamaster ® VL defoamer 1.50 Acrysol ® RM-2020NPRHEUR 30.00 thickener Letdown prepared on low speed mixer Natrosol ® Plus330 (3% in solution in 25.04 water) HMHEC thickener Water 67.76 KUinitially after preparation 99 pH initially after preparation 1.8 ICIinitially after preparation 9.22 Brookfield viscosity 10100 (cps at 1.25sec⁻¹) Actual scale repared (gallons) 50

Example 6

Mixtures A to D described below will require occasional mixing to remainstable.

A B Ingredients lbs/100 gallons lbs/100 gal Grind prepared on Cowlesdisperser Water 272.7 272.7 Tamol ® 1124 AA/HPA dispersant 7.35 7.35Kathon ® LX 1.5% biocide 2.00 2.00 Ti-Pure ® R706 universal-grade TiO₂918.2 918.2 Letdown prepared on low speed mixer Triton ® CF-10surfactant 0 1.0 Propylene glycol 50 50 Foamaster ® VL defoamer 1.5 1.5Ropaque ® Ultra opaque polymer 205.56 205.56 Natrosol ® Plus 330 (3% insolution in 192 113 water) HMHEC thickener Attagel ® 50 attagulpite clay(100% — 5.0 solid) Ammonia hydroxide (28%) 1.96 1.98 KU initially afterpreparation 92 94 pH initially after preparation 0.5 0.5 ICI initiallyafter preparation 8.87 8.75 Brookfield viscosity 23000 27700 (cps at1.25 sec⁻¹) Actual scale prepared (gallons) 57 53 C D Ingredientslbs/100 gallons lbs/100 gallons Grind prepared on Cowles disperserPropylene glycol 50 50 Water 160 160 Tamol ® 1124 AA/HPA dispersant 7.357.35 Kathon ® LX 1.5% biocide 2.00 2.00 Ti-Pure ® R706 universal-gradeTiO₂ 918.2 918.2 Letdown prepared on low speed mixer Foamaster ® VLdefoamer 1.5 1.5 Ropaque ® Ultra opaque polymer 205.56 205.56 Natrosol ®Plus 330 (3% in solution in 80.06 water) HMHEC thickener Natrosol ® 250MHR (3.5% in solution 134.7 in water) HEC thickener Ammonium hydroxide(28%) 1.80 1.86 Water 106.7 50.22 KU initially after preparation 94 98pH initially after preparation 8.68 8.67 ICI initially after preparation0.5 0.8 Brookfield viscosity 18700 28200 (cps at 1.25 sec⁻¹) Actualscale prepared (gallons) 50 50

Example 7

Mixtures A to E described below will require occasional mixing to remainstable.

A B C D E lbs/100 lbs/100 lbs/100 lbs/100 lbs/100 Ingredients gallonsgallons gallons gallons gallons Grind pre- pared on Cowles dis- perserWater 115 115 115 115 93.46 Propylene 50 50 50 50 40.64 glycol Tamol ®20.99 10.49 31.48 41.97 25 59 1254 AA/ MAA dispersant Foamaster ® 2.002.00 2.00 2.00 2.44 VL defoamer Triton ® 1.50 1.50 1.50 1.50 1.63 CF-10surfactant Kathon ® 2.00 2.00 2.00 2.00 1.63 LX 1.5% biocide Ti-Pure ®734.56 734.56 734.56 734.56 596.96 R706 univer- sal-grade TiO₂Foamaster ® 1.50 1.50 1.50 1.50 VL defoamer Ropaque ® 164.44 164.44164.44 164.44 133.64 Ultra opaque polymer Letdown prepared on low speedmixer Res 3083 140.10 140.10 140.10 140.10 245.05 emulsion Texanol ®11.37 11.37 11.37 11.37 15.73 coalescent Acrysol ® 9.6 7.12 5.67 4.127.92 DR-3 HASE thickener Ammonium 2.12 2.34 1.96 1.81 2.28 hydroxide(28%) Water 150.8 152.8 145.55 138.67 144.93 KU initially 100 101 99 9798 after preparation pH initially 8.69 8.54 8.68 8.4 after preparationICI initially 0.9 0.8 0.8 0.7 1.1 after preparation Brookfield 2770029200 31600 29900 23800 viscosity (cps at 1.25 sec⁻¹)

Example 8

Mixtures A and B described below will require constant mixing to remainstable.

A B lbs/100 lbs/100 Ingredients gallons gallons Grind prepared on Cowlesdisperser Water 174.98 174.98 Propylene glycol 62.49 62.49 Tamol ® 731MA/DIB dispersant 36.72 36.72 Foamaster ® VL defoamer 1.87 1.87 Triton ®CF-10 surfactant 2.50 2.50 Kathon ® LX 1.5% biocide 2.50 2.50 Ti-Pure ®R706 universal-grade TiO₂ 918.12 918.12 Letdown prepared on Cowlesdisperser Foamaster ® VL defoamer 1.87 1.87 Ropaque ® Ultra opaquepolymer 205.53 205.53 Letdown on a low speed mixer Natrosol ® Plus 330(3% in solution in 45.09 water) HMHEC thickener Natrosol ® 250 MHR (3.5%in solution 127.69 45.09 in water) HEC thickener Ammonium hydroxide(28%) 1.00 1.34 Water 0 80.99 KU initially after preparation 99 99 pHinitially after preparation 8.69 8.76 ICI initially after preparation1.6 0.8 Brookfield viscosity 20200 22700 (cps at 1.25 sec⁻¹) Actualscale prepared (gallons) 100 100

Supplier Information Material Name Description Supplier Tamol ™ 1124Dispersant Rohm and Haas Company (Philadelphia, PA) Tamol ™ 1254Dispersant Rohm and Haas Company (Philadelphia, PA) Tamol ™ 731 MA/GIBDispersant Rohm and Haas Company (Philadelphia, PA) Acrysol ™ DR-1 HASEThickener Rohm and Haas Company (Philadelphia, PA) Acrysol ™ DR-3 HASERohm and Haas Company Thickener/Rheology (Philadelphia, PA) ModifierAcrysol ™ DR-73 HASE Thickener Rohm and Haas Company (Philadelphia, PA)Acrysol ™ RM-2020 HEUR Rohm and Haas Company NPR Thickener/Rheology(Philadelphia, PA) Modifier Rhoplex ™ SG-10M Emulsion Polymer Rohm andHaas Company Binder (Philadelphia, PA) RES 3083 Emulsion Polymer Rohmand Haas Company Binder (Philadelphia, PA) Kathon ™ LX 1.5% Biocide Rohmand Haas Company (Philadelphia, PA) Triton ™ CF-10 Surfactant UnionCarbide Corporation (Danbury, CT) Foamaster ™ VL Defoamer HenkelCorporation (King of Prussia, PA) Ti-Pure ™ R-706 Titanium Dioxide E. I.Dupont de Nemours and Co., Inc. (Wilmington, DE) Ti-Pure ™ R-900Titanium Dioxide E. I. Dupont de Nemours and Co., Inc. (Wilmington, DE)Ti-Pure ™ R-902 Titanium Dioxide E. I. Dupont de Nemours and Co., Inc.(Wilmington, DE) Kronas ® 2102 Universal Grade Kronas (Houston, TX)Titanium Dioxide Ropaque ® Ultra Opaque Rohm and Haas Synthetic/Polymer(Philadelphia, PA) Texanol ™ Coalescent Eastman Chemical (Kings Port,TN) Natrosol ® HEC Thickner Hercules (Wilmington, DE) Natrosol ® Plus430 HMHEC Thickener Hercules (Wilmington, DE) Natrosol ® Plus 330 HMHECThickener Hercules (Wilmington, DE) Natrosol ® 250 MHR HEC ThickenerHercules (Wilmington, DE) Attrgel ® 50 Attapulgite Clay Engelhardt(Edison, NJ)

1. A fluid opacifying pigment mixture having a titanium dioxide pigmentvolume concentration of about 40 to about 100%, a titanium dioxidevolume solids content of at least about 15%, and a Stormer viscosity ofabout 50 to about 250 KU, which mixture comprises: (a) about 600 toabout 1500 lbs/100 gallons of at least one universal-grade titaniumdioxide; (b) about 0.2 to about 20 lbs/100 gallons of at least onehydrophobically-modified ethylene oxide-urethane polymer (HEUR)thickener selected from the group consisting of: (i) a HEUR having aC₄-C₁₂ hydrophobe and a molecular weight of about 10,000 to about200,000, (ii) a HEUR having a C₆-C₃₀ hydrophobe and a molecular weightof about 10,000 to about 200,000, and (iii) combinations thereof, (c)about 1.5 to about 16 lbs/100 gallons of at least one dispersantselected from the group consisting of a maleic acid/diisobutylenecopolymer, a butyl methacrylate/methacrylic acid copolymer, and anacrylic acid/hydroxypropyl acrylate copolymer; and (d) water.
 2. A fluidopacifying pigment mixture having a titanium dioxide pigment volumeconcentration of about 40 to about 100%, a titanium dioxide volumesolids content of at least about 15%, and a Stormer viscosity of toabout 50 to about 250 KU, which mixture comprises: (a) about 600 toabout 1500 lbs/100 gallons of at least one interior-grade titaniumdioxide; (b) about 0.3 to about 5 lbs/100 gallons of at least onehydrophobically modified, alkali-soluble emulsion (HASE) thickenerhaving a C₆-C₂₂ hydrophobe and a molecular weight of about 10,000 toabout 7,000,000; (c) about 1.8 to about 23 lbs/100 gallons of at leastone dispersant selected from the group consisting of a maleicacid/diisobutylene copolymer, a butyl methacrylate/methacrylic acidcopolymer, an acrylic acid/hydroxypropyl acrylate copolymer and apolyacrylic acid; and (d) water.
 3. A fluid opacifying pigment mixturehaving a titanium dioxide pigment volume concentration of about 40 toabout 100%, a titanium dioxide volume solids content of at least about15%, and a Stormer viscosity of about 50 to about 250 KU, whichcomprises: (a) about 600 to about 1500 lbs/100 gallons of at least oneuniversal-grade titanium dioxide; (b) about 2 to about 6 lbs/100 gallonsof at least one hydrophobically-modified hydroxyalkyl cellulosethickener having a molecular weight of about 10,000 to about 10,000,000;(c) about 1.8 to about 23 lbs/100 gallons of at least one polyacrylicacid dispersant; and (d) water.
 4. A fluid opacifying pigment mixturehaving a titanium dioxide pigment volume concentration of about 40 toabout 100%, a titanium dioxide volume solids content of at least about15%, and a Stormer viscosity of about 50 to about 250 KU, which mixturecomprises: (a) about 600 to about 1500 lbs/100 gallons of at least oneuniversal-grade titanium dioxide; (b) about 0.2 to about 10 lbs/100gallons of at least one hydrophobically-modified hydroxyalkyl cellulosethickener having a molecular weight of about 10,000 to about 10,000,000;(c) about 2 to about 10 lbs/100 gallons of at least onehydrophobically-modified ethylene oxide-urethane polymer (HEUR)thickener having a C₄-C₃₀ hydrophobe and a molecular weight of about10,000 to about 200,000; (d) about 3.0 to about 22.5 lbs/100 gallons ofat least one maleic acid/diisobutylene copolymer dispersant; and (e)water.
 5. A fluid opacifying pigment mixture having a titanium dioxidepigment volume concentration of about 40 to about 100%, a titaniumdioxide volume solids content of at least about 15%, and a Stormerviscosity of about 50 to about 250 KU, which mixture comprises: (a)about 600 to about 1500 lbs/100 gallons of at least one universal-gradetitanium dioxide; (b) about 0.2 to about 10 lbs/100 gallons of at leastone hydrophobically-modified hydroxyalkyl cellulose thickener having amolecular weight of about 10,000 to about 10,000,000; (c) about 2 toabout 10 lbs/100 gallons of at least one hydrophobically-modifiedethylene oxide-urethane polymer (HEUR) thickener having a C₄-C₃₀hydrophobe and a molecular weight of about 10,000 to about 200,000, (d)about 0.5 to about 22.5 lbs/100 gallons of at least one acrylicacid/hydroxypropyl acrylate dispersant; and (e) water.
 6. A fluidopacifying pigment mixture having a titanium dioxide pigment volumeconcentration of about 40 to about 100%, a titanium dioxide volumesolids content of at least about 15%, and a Stormer viscosity of about50 to about 250 KU, which mixture comprises: (a) about 600 to about 1500lbs/100 gallons of at least one universal-grade titanium dioxide; (b)about 0.2 to about 10 lbs/100 gallons of at least one hydroxyalkylcellulose thickener having a molecular weight of about 10,000 to about10,000,0000 or a hydrophobically-modified hydroxyalkyl cellulosethickener having a molecular weight of about 10,000 to about 10,000,000;(c) about 0.5 to about 22.5 lbs/100 gallons of at least one acrylicacid/hydroxypropyl acrylate dispersant; and (d) water.
 7. A fluidopacifying pigment mixture having a titanium dioxide pigment volumeconcentration of about 40 to about 100%, a titanium dioxide volumesolids content of at least about 15%, and a Stormer viscosity of about50 to about 250 KU, which mixture comprises: (a) about 600 to about 1500lbs/100 gallons of at least one universal-grade titanium dioxide; (b)about 0.3 to about 5 lbs/100 gallons of at least onehydrophobically-modified, alkali-soluble or alkali-swellable emulsion(HASE) thickener having a C₆-C₂₂ hydrophobe and molecular weight ofabout 10,000 to about 7,000,000; (c) about 1.2 to about 45 lbs/100gallons of at least one polyacrylic acid dispersant; and (d) water.
 8. Afluid opacifying pigment mixture having a titanium dioxide pigmentvolume concentration of about 40 to about 100%, a titanium dioxidevolume solids content of at least about 15%, and a Stormer viscosity ofabout 50 to about 250 KU, which mixture comprises: (a) about 600 toabout 1500 lbs/100 gallons of at least one universal-grade titaniumdioxide; (b) about 0.5 to about 10 lbs/100 gallons of ahydrophobically-modified hydroxyalkyl cellulose thickener having amolecular weight of about 10,000 to about 10,000,000; (c) about 1.2 toabout 18 lbs/100 gallons of at least one maleic acid/diisobutylenedispersant; and (d) water.
 9. A fluid opacifying pigment mixture havinga titanium dioxide pigment volume concentration of about 40 to about100%, a titanium dioxide volume solids content of at least about 15%,and a Stormer viscosity of about 50 to about 250 KU, which mixturecomprises: (a) about 600 to about 1500 lbs/100 gallons of at least oneuniversal-grade titanium dioxide; (b) about 0.1 to about 3 lbs/100gallons of at least one hydrophobically-modified, alkali-soluble oralkali-swellable emulsion (HASE) thickener having a C₆-C₂₂ hydrophobeand a molecular weight of about 10,000 to about 7,000,000; (c) about 0.6to about 22.5 lbs/100 gallons of at least one acrylic acid—hydroxypropylacrylate dispersant; and (d) water.
 10. A fluid opacifying pigmentmixture having a titanium dioxide pigment volume concentration of about40 to about 100%, a titanium dioxide volume solids content of at leastabout 15%, and a Stormer viscosity of about 50 to about 250 KU, whichmixture comprises: (a) about 600 to about 1500 lbs/100 gallons of atleast one universal-grade titanium dioxide; (b) about 0.1 to about 3lbs/100 gallons of at least one hydrophobically-modified, alkali-solubleor alkali-swellable emulsion (HASE) thickener having a C₆-C₂₂ hydrophobeand a molecular weight of about 10,000 to about 7,000,000; (c) about 0.6to about 45 lbs/100 gallons of at least one maleic acid/diisobutylenecopolymer dispersant; and (d) water.
 11. A fluid opacifying pigmentmixture, a titanium dioxide pigment volume concentration of about 40 toabout 100%, a titanium having dioxide volume solids content of at leastabout 15%, and a Stormer viscosity of about 50 to about 250 KU, whichmixture comprises: (a) about 600 to about 1500 lbs/100 gallons of atleast one interior-grade titanium dioxide; (b) about 0.2 to about 20lbs/100 gallons of at least one hydrophobically-modified ethyleneoxide-urethane polymer (HEUR) thickener selected from the groupconsisting of a HEUR having a C₄-C₁₂ hydrophobe and a molecular weightof about 10,000 to about 200,000, a HEUR having a C₆-C₃₀ hydrophobe anda molecular weight of about 10,000 to about 200,000, and combinationsthereof; (c) about 1.2 to about 18 lbs/100 gallons of at least onemaleic acid/diisobutylene dispersant; and (d) water.
 12. The mixture ofclaims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11, which further comprises oneor more additives selected from the group consisting of a defoamer, asurfactant, a coalescent, a base, a biocide, a mildewcide, aco-dispersant, a polymeric binder, and a voided latex polymer.
 13. Themixture of claim 6, further comprising about 2 to about 12 lbs/100gallons of at least one hydrophobically-modified ethylene oxide-urethanepolymer (HEUR) thickener having a C₄-C₃₀ hydrophobe and a molecularweight of about 10,000 to about 200,000 or at least one clay thickener.14. The mixture of claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 12, whereinthe pigment volume concentration is about 50 to 100%.
 15. The mixture ofclaim 14, wherein the pigment volume concentration is about 60 to about100%.
 16. The mixture of claim 15, wherein the pigment volumeconcentration is about 70 to about 100%.
 17. The mixture of claim 16,wherein the pigment volume concentration is about 80 to about 100%. 18.The mixture of claim 17, wherein the pigment volume concentration isabout 90 to about 100%.
 19. The mixture of claims 6-11, wherein saidmixing is carried out using an impeller, a recirculator, a shaker, amill, a rotator, a bubbler, a sonicator, a pump or combinatiuonsthereof.